Systems and methods for scalable perovskite device fabrication

ABSTRACT

Continuous processes for fabricating a perovskite device are described that include using a doctor blade for continuously forming a perovskite layer and using a conductive tape lamination process to form an anode or a cathode layer on the perovskite device.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application claims the benefit of U.S. Provisional PatentApplication No. 62/108,873, filed Jan. 28, 2015, which is incorporatedherein by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT

This invention was made with Government support under contractDE-EE0006709 awarded by the Department of Energy (DOE) and undercontract HDTRA1-14-1-0030 awarded by the Defense Threat Reduction Agency(DTRA). The Government has certain rights in this invention.

BACKGROUND

The Sun deposits 120,000 terawatts (TW) of power onto the Earth'ssurface. This is more than the 13 TW of total power that is currentlyused by the planet's population. Photovoltaics (PV) convert solar energyinto direct current electricity using semiconducting materials thatexhibit the photovoltaic effect. The photovoltaic effect includesphotons of light exciting electrons into a higher state of energy,allowing them to act as charge carriers for an electric current. Aphotovoltaic system can employ solar panels including a number of solarcells to supply usable solar power.

Organometal trihalide perovskites (OTPs, e.g., CH₃NH₃PbX₃, X═Cl, Br, Ior a mixed halide) can be excellent low-cost, earth-abundantphotovoltaic materials due to proper bandgap, excellent crystallinity,and strong absorption. In addition, OTPs have advantageousoptoelectronic properties, such as a very large carrier mobilitycomparable to silicon, bipolar transport, and large charge carrierdiffusion length, which enables high performance devices with thetraditional planar heterojunction (PHJ) structure.

Perovskite photovoltaic devices (PPVs) have been demonstrated to haveall the desired properties of organic photo voltaic devices (OPVs),which have strong market potential in military and civilianapplications, including for flexible, wearable, lightweight, andportable chargers for electronics, building-integrated photovoltaics(BIPVs), and off-grid power generation. PPVs have shown all three maincompetencies of that OPVs have over other photovoltaic technologies: 1)PPVs can be made on flexible plastic substrates; 2) PPVs can befabricated with low cost materials and a solution process; 3) Perovskitematerials have tunable color and bandgaps with semitransparency, whichallows for the integration of PPVs into buildings. State-of-the-art PPVdevices can have an efficiency of 20%, but they need to reach 25% tocompete with other commercialized thin film solar cell technologies inorder to make them commercially viable. The thermodynamic efficiencylimit of single junction PPVs can be 38% based on its bandgap.

High mobility and lifetime is important for photonic devices because thelight-generated electrons and holes can move longer distances to beextracted as current, thus avoiding release of their energy as heat bythe recombination. High mobility and high carrier lifetimes are alsocrucial for photo detectors. For example, in an organic/inorganic hybridphoto detector, if one type of carriers (e.g., electrons) can be trappedlonger, the other type of carriers (e.g., holes) thus circulates manytimes with high mobility through the polymer matrix or network. In thiscase, ultra-high gain (gain may be defined by the ratio of the lifetimeof the trapped electrons and the transit time of holes), can beobtained.

Despite the high efficiency reported in devices fabricated by thermalevaporation, the complicated controlling of the non-stoichiometry ofOTPs such as CH₃NH₃PbI_(3-x)Cl_(x) by co-evaporation under high vacuumdims its advantage of being low cost. Low temperature solution processesare attractive in the fabrication of electronic devices, especiallylarge-area solar cells, for reducing fabrication costs.

Thin film photovoltaic devices based on OTPs are a promising area ofrenewable energy research. These solar cells utilize light harvestingthin films include a polycrystalline perovskite with a structure ofAMX₃, where A is an organic and/or inorganic cation, (e.g.,methylammonium (CH₃NH₃+(MA+), NH2CH═NH2+,(FA+)Cs+)), the M is a metalcation, (e.g., Pb2+, Sn2+,), and X is a halide anion (e.g., I—, Cl—,and/or Br—). Power conversion efficiencies (PCE) of perovskite solarcells using these methods can exceed 16%. The solution processability ofOTPs enables the capitalization of development in organic photovoltaics(OPVs) for low-cost, high-throughput production of OPT solar panels onboth rigid and flexible substrates. However, current methods infabricating high efficiency perovskite devices (e.g., solar cells), suchas spin-coating or thermal evaporation, are not compatible withlarge-scale production processes, such as a roll-to-roll process. Thereis lack of a film deposition methodology for perovskite films which canbe compatible with roll-to-roll fabrication processes for large scaleproduction of perovskite solar cell panels while still achieving highperformance.

Accordingly, there is a need for improved photoactive devices includingOTPs as an active layer as well as improved methods for fabricating suchphotoactive devices.

SUMMARY

Accordingly, the present disclosure generally provides systems andmethods for fabricating photoactive device structures, and moreparticularly to photoactive devices including a photoactive perovskitefilm layer and systems and methods for fabricating the same. In certainembodiments, a conductive tape lamination process is used to form ananode or a cathode layer on the photoactive device.

In certain embodiments, doctor blade coating techniques are used tofacilitate formation of a photoactive layer and/or other material layersduring the fabrication processes. Utilizing a doctor blade coatingprocess is advantageous because of increased scalability for perovskitedevice roll-to-roll production, simplicity, and cost effectiveness.Furthermore, doctor-blading also provides advantages due tohigh-throughput deposition, high material usage, and application ontoflexible substrates. Perovskite films and devices fabricated using adoctor-blade coating can have advantageously long carrier diffusionlengths (e.g., up to 3 μm thick) due to the dramatically higher carriermobility in the blade-coated films. Such doctor-blade deposition can beutilized for large area perovskite cells fabricated with high volumeroll-to-roll production.

In certain embodiments, conductive tape lamination techniques are usedto facilitate formation of conductive device layers as an anode layerand/or a cathode layer in the fabrication processes. Lamination usingconductive tape advantageously allow for reduced fabrication andmaterial costs and increased protection and stability of the device(s)formed.

According to an embodiment, a process or method for fabricating aperovskite device is provided. The process typically includes receivinga substrate, applying a perovskite precursor solution onto thesubstrate, and linearly swiping the perovskite precursor solution usinga doctor blade to form a perovskite film on the substrate. In certainaspects, the process includes simultaneously heating the substrate whileapplying and linearly swiping the perovskite precursor solution. Incertain aspects, heating the substrate includes heating the substrate toa temperature in a range of between about 50° C. and about 180° C. Incertain aspects, heating the substrate includes heating the substrate toabout 125° C. In certain aspects, the substrate is moving and the doctorblade is stationary. In certain aspects, the substrate is moving at arate of about 0.75 cm/sec to about 75 cm/sec relative to the doctorblade. In certain aspects, the substrate is stationary and wherein thedoctor blade moves relative to the substrate. In certain aspects,applying the perovskite precursor solution onto the substrate includesdispensing between about 10 μL and about 20 μL of perovskite precursorsolution for every 2.25 mm² of substrate.

In certain aspects, the precursor solution includes a lead halide (e.g.,PbI₂, PbBr₂ or PbCl₂) and at least one of a methylammonium halide (e.g.,CH₃NH₃I, CH₃NH₃Br, CH₃NH₃Cl) or a formamidinium halide (e.g., CH(NH₂)₂I,CH(NH₂)₂Br, CH(NH₂)₂Cl) dissolved in dimethylformamide (DMF) or Methylsulfoxide (DMSO) or a mixture of two or more thereof in any ratio.

In certain aspects, the substrate comprises indium tin oxide (ITO) orother transparent conductive electrodes. In certain aspects, the processfurther includes heating the perovskite device, and rolling a conductivetape onto the perovskite device, wherein the conductive tape includes anadhesive material and a conductive material. In certain aspects, heatingthe perovskite device includes heating the perovskite device to atemperature between about 50° C. and about 175° C.

According to another embodiment, a process or method for continuouslylaminating a perovskite device is provided. The process typicallyincludes forming a perovskite device by doctor blade coating aperovskite precursor solution onto a substrate, heating the perovskitedevice, and rolling or otherwise applying a conductive tape onto theperovskite device, wherein the conductive tape includes an adhesivematerial and a conductive material In certain aspects, heating theperovskite device includes heating the perovskite device to atemperature between about 50° C. and about 175° C. In certain aspects,the conductive material includes at least one of aluminum, copper,nickel, gold, or silver. In certain aspects, the substrate comprisesindium tin oxide (ITO) or other transparent conductive electrodematerials.

According to yet another embodiment, a process or method for fabricatinga perovskite device is provided. The process typically includes heatingan indium tin oxide (ITO) substrate, applying a perovskite precursorsolution onto the ITO substrate, linearly swiping the perovskiteprecursor solution using a doctor blade to form a perovskite film,simultaneously thermoannealing and solvent annealing the perovskitefilm, depositing a charge transport layer on the perovskite film,thermoannealing the charge transport layer, depositing a fullerene layeron the charge transport layer, and applying an conductive layer to thefullerene layer. In certain aspects, the ITO substrate includes an ITOlayer and a hole transport layer. In certain aspects, the hole transportlayer includes at least one of PEDOT:PSS, TPD plus TPACA or PTAA, orother hole transport material or materials. In certain aspects, the holetransport layer may be processed by an argon plasma process to enhancethe adhesion of the solution thereto.

In certain aspects, the precursor solution includes a lead halide (e.g.,PbI₂, PbBr₂ or PbCl₂) and at least one of a methylammonium halide (e.g.,CH₃NH₃I, CH₃NH₃Br, CH₃NH₃Cl) or a formamidinium halide (e.g., CH(NH₂)₂I,CH(NH₂)₂Br, CH(NH₂)₂Cl) dissolved in dimethylformamide (DMF) or Methylsulfoxide (DMSO) or a mixture of two or more thereof in any ratio.

In certain aspects, the ITO substrate is linearly moving. In certainaspects, applying the perovskite precursor solution onto the ITOsubstrate includes dropping or dispensing between about 10 μL and about20 μL of perovskite precursor solution for every 2.25 mm2 of ITOsubstrate. In certain aspects, simultaneously thermoannealing andsolvent annealing the perovskite film includes thermoannealing at about100° C. for about 60 minutes. In certain aspects, simultaneouslythermoannealing and solvent annealing the perovskite film includessolvent annealing with about 10 μL of DMF.

In certain aspects, depositing a charge transport includes depositing aPC₆₀BM layer includes depositing PC60BM dissolved in 2% by weight1,2-dichlorobenzene (DCB) solution. In certain aspects, thermoannealingthe PC₆₀BM charge transport layer includes thermoannealing at about 100°C. for about 60 minutes. In certain aspects, applying a conductive layerto the fullerene layer includes depositing a layer of conductive metalon the fullerene layer. In certain aspects, applying a conductive layerto the fullerene layer includes applying a conductive tape onto thefullerene layer. In certain aspects, depositing a PC₆₀BM layer includesdepositing PC₆₀BM dissolved in 2% by weight 1,2-dichlorobenzene (DCB)solution. In certain aspects, depositing a charge transport layerincludes depositing one of a PC₆₀BM layer, a fullerene derivative layer,a ZnO layer, a SnO₂ layer or a TiO₂ layer.

Reference to the remaining portions of the specification, including thedrawings and claims, will realize other features and advantages of thepresent invention. Further features and advantages of the presentinvention, as well as the structure and operation of various embodimentsof the present invention, are described in detail below with respect tothe accompanying drawings. In the drawings, like reference numbersindicate identical or functionally similar elements.

DRAWINGS

The detailed description is described with reference to the accompanyingfigures. The use of the same reference numbers in different instances inthe description and the figures may indicate similar or identical items.

FIG. 1 is an environmental process view illustrating a continuousprocess for fabricating a perovskite device using a doctor blade andlamination of a conductive tape, in accordance with an embodiment of thepresent disclosure.

FIG. 2 is an isometric environmental process view illustrating acontinuous process for fabricating a perovskite device using a doctorblade, in accordance with an embodiment of the present disclosure.

FIG. 3 is an environmental process view illustrating a continuousprocess for fabricating a perovskite device using a rolling andlaminating process for applying a conductive tape, in accordance with anembodiment of the present disclosure.

FIG. 4 is a flow diagram illustrating an embodiment of a continuousprocess for fabricating a perovskite solar device using a doctor blade,such as the perovskite device illustrated in FIGS. 1 through 3.

FIG. 5 is a flow diagram illustrating an embodiment of a continuousprocess for laminating conductive tape onto a perovskite device, such asthe perovskite device illustrated in FIGS. 1 through 3.

FIG. 6 is a flow diagram illustrating a continuous process forfabricating a perovskite device according to an embodiment.

DETAILED DESCRIPTION

The present disclosure generally provides systems and methods forfabricating photoactive device structures, and more particularly tosystems and methods for fabricating perovskite device including aphotoactive perovskite film layer. In certain embodiments, a conductivetape lamination process is used to form an anode or a cathode layer onthe photoactive device.

In certain embodiments, doctor blade coating techniques are used tofacilitate formation of a photoactive layer and/or other material layersduring the fabrication processes. Utilizing a doctor blade coatingprocess is advantageous because of increased scalability for perovskitedevice roll-to-roll production, simplicity, and cost effectiveness.Furthermore, doctor-blading also provides advantages due tohigh-throughput deposition, high material usage, and application ontoflexible substrates. Perovskite films and devices fabricated using adoctor-blade coating can have advantageously long carrier diffusionlengths (e.g., up to 3 μm thick) due to the dramatically higher carriermobility in the blade-coated films. Such doctor-blade deposition can beutilized for large area perovskite cells fabricated with high volumeroll-to-roll production.

In certain embodiments, conductive tape lamination techniques are usedto facilitate formation of conductive device layers as an anode layerand/or a cathode layer in the fabrication processes. Lamination usingconductive tape advantageously allow for reduced fabrication andmaterial costs and increased protection and stability of the device(s)formed.

FIGS. 1 through 3 illustrate embodiments of a perovskite devicestructure 124 and methods for fabricating the perovskite device 124utilizing a doctor blade coating process and a conductive tapelaminating process. It should be appreciated that the doctor bladecoating process and a conductive tape laminating process need not beused together, e.g., a device may be formed with the doctor bladecoating process but without the lamination process, or a device could befabricated using the lamination process, but not the blade-coatingprocess. However, the description herein will generally refer to devicesformed using both the blade coating process and the lamination process.

In certain embodiments, perovskite device 124 can be fabricated using aperovskite device fabrication apparatus 100, as illustrated in FIGS. 1through 3. As shown in FIGS. 1 and 2, an embodiment of a perovskitedevice fabrication apparatus 100 includes at least one heating device102 (three shown), at least one doctor blade 116 (two shown), and atleast one rod assembly 120. In an embodiment, a heating device 102 caninclude a device configured to provide heat to a substrate 108 (e.g., anITO substrate 108 as shown in FIG. 1 or to a different substrate such asa steel or silicon substrate 104 upon which the substrate 108 may belocated or attached. The substrate 108 may be stationary with respect toeach heater 102, or the substrate 108 may continuously move in a linearconfiguration relative to the heaters 102. Some examples of a heatingdevice 102 can include a convective and/or radiative heater or heatingelement. It is contemplated that a heating device 102 may include otherheaters using other heating methods.

The perovskite device fabrication apparatus 100 can include at least onedoctor blade 116 configured to deposit, form, and/or evenly distribute amaterial 118 applied to or dropped onto the substrate 108 (e.g., ITOsubstrate) or onto perovskite device 124, e.g., a charge transport layermaterial 112 applied to or dropped onto perovskite film layer 110. Adoctor blade 116 may include a blade, such as a glass blade, and/ordevice for removing excess accumulated material from a surface.Advantages of utilizing doctor blading include scalability forroll-to-roll production, simplicity, and cost effectiveness.Additionally, doctor-blading can be adapted for high throughputdeposition, high material usage, and material application onto flexiblesubstrates. In an embodiment, a doctor blade 116 can remove excessperovskite (e.g., MAPbI₃) precursor solution from the surface ofsubstrate 108 as the precursor solution is dropped on the substrate 108.In another embodiment, the same or another doctor blade 116 can removeexcess charge transport material 112 from the surface of a perovskitefilm 110.

In one embodiment, the perovskite device fabrication apparatus 100includes a rod assembly 120 configured for applying pressure and/or heatto a conductive tape 114 during a lamination process. The rod assembly120 can include a rod and/or a roller configured with a harness or otherbiasing mechanism to apply pressure to a conductive tape 114 as theconductive tape 114 is continuously rolled and laminated to the surfaceof a charge transport material 112 and/or perovskite device 124.

FIG. 2 illustrates an apparatus 100 for use in doctor blade coating oneor more materials to form a perovskite device according to anembodiment. As shown in one embodiment, device 110 includes a heatconductive holding substrate layer 104, such as a silicon or steelsubstrate, and a pair of guiding elements 106, which may be glass orsilicon layers arranged to facilitate doctor-blade coating as shown. Forexample, a substrate 108 (e.g., an ITO substrate) may be located orpositioned between the pair of guiding elements 106 as shown. A drop ofmaterial 118 (e.g., perovskite precursor solution) applied to thesubstrate 108 is doctor blade coated using doctor blade 116. In oneembodiment, the substrate 108 may be stationary, wherein the doctorblade 116 moves linearly across the substrate 108 using the guideelements 106 to control process parameters. In another embodiment, thedoctor blade 116 may be stationary, wherein the substrate 108 moveslinearly underneath the blade 116 using the guide elements 106 tocontrol process parameters. For example, the guide elements may have aspecific height such that the height difference between the substrate108 and the guide elements controls the thickness of the perovskitelayer 110 produced. Mechanical elements such as linear actuators andmotors may be coupled with the blade 116 and/or the substrate 108 and/orholding substrate 104 to control movement of the blade 116, thesubstrate 108 and/or holding substrate 104.

FIG. 3 illustrates a rolling and laminating process for applying aconductive tape to a perovskite device 124 in accordance with anembodiment of the present disclosure. As shown roller element 120 rollsand applies a lamination layer 114, which may include a conductive tapeto the device structure 124. As shown, the tape 114 is applied to acharge transport layer 112, however, it should be appreciated that thetape layer may be applied directly to perovskite layer 110, or to anyother layer in the device structure to be laminated.

FIG. 4 illustrates a process 400 for fabricating a photoactiveperovskite device, such as device 124 as shown in FIGS. 1 through 3. Thedevice formed may be a solar cell, photodetector or solar panel or otherphotoactive device. In some implementations, process 400 may beperformed in a N₂ atmosphere. In step 402, a substrate (e.g., substrate108) is received. In certain embodiments, receiving substrate 108 caninclude receiving an ITO substrate assembly 122 in a continuous fashion(e.g., a continuous assembly production process) or in a discreteprocess (e.g., sheets or panels of an ITO substrate assembly that areprocessed using the perovskite device fabrication apparatus 100 inbatches. In one specific embodiment, receiving the substrate assemblycan include receiving a moving substrate 108. In another embodiment,receiving can include positioning a stationary substrate.

In step 404, a perovskite precursor solution is dropped onto thesubstrate 108. In one embodiment, the perovskite precursor solutionincludes PbI₂ and a methylammonium halide, such as methylammonium iodide(e.g., CH₃NH₃I, MAI), mixed in dimethylformamide (DMF). In one specificembodiment, a perovskite precursor solution can be dropped onto an ITOsubstrate 108 including a hole transport material or a hole transportmaterial layer. Dispensing a perovskite precursor solution can includeusing a continuous liquid dispenser or a syringe to apply a drop oramount of material. In a specific embodiment, about 10 to about 20 μL ofperovskite precursor solution can be dropped for about every 2.25 mm² ofITO substrate 108.

Other processes, such as spin coating, may require as much as 50-100 μLof the same perovskite precursor solution over the same substrate area.

Purification of the perovskite precursor solution (e.g., MAI) may beimportant for doctor-blade coating of a smooth perovskite film 110.Perovskite precursor solutions made from PbI₂ and a non-purified MAI mayimmediately become visibly cloudy even after filtration of precursorsolution with a pore size filter. This may be caused by the reaction ofPb²⁺ with an impurity (e.g., PO₂ ³⁻ that forms insoluble PbPO₃particles). In some implementations, HI and CH₃NH₂ (MA) solutions can beused as the starting materials for MAI synthesis. While an HI solutioncontains 2% H₃PO₂ (e.g., from Sigma-Aldrich) as a stabilizer to preventthe decomposition of HI, H₃PO₂ may also react with MA to form (MA)₃PO₂,which may be difficult to remove using a regular MAI washing processbecause of its high solubility in washing solvent (e.g., ethanol). Inorder to eliminate impurities, MAI may be purified by recrystallization(i.e, cooling a high-temperature supersaturated MAI solution to obtainpurified MAI crystals). Due to very high solubility of (MA)₃PO₂ inethanol and the low percentage of (MA)₃PO₂ in MAI, (MA)₃PO₂ is notrecrystallized and remains in the solution. Perovskite precursorsolutions made from PbI₂ with purified MAI in DMF can appear very clearwithout any visible appearance change after storage for several monthsat ambient conditions. Perovskite films formed using non-purified MAIare generally non-continuous with micrometer wide gaps between the largedomains, which may be caused by impurities pushed toward the edgesduring the grain growing process. In sharp contrast, perovskite filmsdeposited from purified MAI are often absent of gaps between bigdomains.

In step 406, the perovskite precursor solution is doctor-bladed, e.g.,linearly swiped using a doctor blade, to form layer 110. For example, ablade 116 (e.g., a glass blade) may be moved across the perovskitesolution 118 dropped on the substrate, or the blade 116 may bestationary and the substrate, with the dropped perovskite solution, maybe moved relative to the blade 116. In one embodiment, a perovskiteprecursor solution can be swiped linearly by a doctor blade 116 at ahigh speed of about 0.75 cm/s (27 m/hour) resulting in a perovskite film110. The relative rate of motion of the blade and the substrate 108 maybe at a linear rate of between about 0.1 cm/sec and about 1.0 cm/sec to10 cm/sec to 75 cm/sec or greater. In one specific embodiment, therelative rate of motion is about 0.75 cm/sec. It is contemplated thatother rates may be utilized when scaling the process. The rate of motionof the doctor blade 116 and/or the substrate 108 may be varied. Thedoctor blade 116 functions, in certain aspects, to remove excessperovskite precursor solution 118 and smooth the remaining perovskiteprecursor solution. A high blading speed is advantageous whenfabricating large area perovskite devices, such as solar panels, with ahigh throughput. The thickness of the perovskite film 110 duringdoctor-blade coating may be controlled by perovskite precursor solutionconcentration, blading speed and the relative spacing between thedoctor-blade 116 and the substrate 108. In some embodiments, thesubstrate 108 can be maintained at an elevated temperature duringdoctor-blade coating for the formation of a smooth, pin-hole freeperovskite film 110. During doctor-blade coating, the substratetemperature can be an important parameter for creating uniform, smoothand pin-hole free perovskite films. When a substrate, e.g., an ITOsubstrate, is held at a temperature much lower than the boiling point ofDMF (about 153° C.) or DMSO (about 189° C.), the perovskite film dryingtime may be too long and may cause slow crystallization of theperovskite, which in turn may create a rough, discontinuous perovskitefilm 110. For example, a perovskite film formed at 100° C. may benon-uniform and may contain numerous μm-wide pinholes, which yields lowdevice power conversion efficiency (PCE) (e.g., below 7%). However,quick drying of a perovskite film (e.g., within about 2 seconds) cancreate uniform and continuous perovskite films. In certain embodiments,therefore, the substrate is held at a temperature in the range ofbetween about 100° C. and about 190° C. In one example, a perovskitefilm 110 deposited at about 135° C. can be continuous and smooth. Toohigh temperature is avoided because it may cause rapid decomposition ofMAPbI₃ within the perovskite precursor solution.

A blade-coated perovskite film can have a unique domain structure withvery large polygon shape domains having a lateral size in the order ofabout 80 μm to about 250 μm. By controlling the substrate temperature,blading speed, perovskite precursor solution concentration (betweenabout 10% (i.e., 100 mg perovskite in 1 ml solvent) to about 60%, and/orusing purified precursor (e.g., MAI mixed with a PbI₂) solution, a largearea perovskite film disposed on an substrate 101, e.g., ITO substrate,can be coated with a perovskite film having a thickness in the range offrom about 0.2 μm to over 10 μm. Lower concentration of the precursorsolution in the range of about 10% to about 35% can result in aconcentric ring structure superimposed in each of the polygon shapedomains, giving a vivid colorful perovskite film observable by the nakedeye.

In certain embodiments, perovskite device 124 may be processed toinclude an electrode layer opposite the substrate to act as an anode orcathode (the substrate, e.g., ITO, may act as the cathode or anode,respectively). In one embodiment, conventional conductive materialdeposition techniques may be used to form a conductive layer, e.g.,deposition of a metal layer or conductive layer. In another embodiment,a conductive tape may be applied as will be described below.

As shown in FIG. 5, process 500 illustrates a process for laminating aconductive tape 114 onto a perovskite device, e.g., perovskite device124 (FIG. 3) according to an embodiment. Process 500 may be performed ina N₂ atmosphere. In step 502, a perovskite device is formed, e.g., bydoctor-blading a perovskite precursor solution onto a substrate asdescribed herein, or otherwise formed, or provided for lamination.

In step 504, the perovskite film or device is heated. In an embodiment,at least one heater device 102 (FIG. 1) can be used to heat thesubstrate 108, the perovskite film 110, the perovskite device 124,and/or the perovskite device fabrication apparatus 100. For example, aperovskite device 124 with a perovskite film 110 can be heated to about60-100° C. Heating the substrate 108 and/or the perovskite device 124may improve contact between a subsequently applied conductive tape 114and the perovskite film 110 or other material layer.

In step 506, conductive tape 114 is rolled and laminated onto the heatedperovskite device. By replacing a traditional metal electrode with aconductive tape 114, the cost of a perovskite device 124 can bedramatically reduced. In certain embodiments, conductive tape 114 mayinclude an adhesive material (e.g., acrylic, etc.) and a conductivematerial (e.g., aluminum, copper, nickel, gold, silver, etc.). In oneembodiment, conductive tape 114 is rolled onto a perovskite device 124and/or a perovskite film 110 (e.g., as a cathode or an anode) using arod assembly 120 (e.g., a rod, roller, etc.) with a harness and pressureor biasing mechanism to provide sufficient pressure to apply the tape114. In some embodiments, a charge transport material 112 may bedeposited on the perovskite film 110 before the rolling and/orlamination of a conductive tape 114. In other embodiments, chargetransport material 112 may be integrated into the conductive tape 114 asa cathode or an anode. Examples of useful charge transport materialsmight include fullerene (C60), fullerene self-assembly (C60-SAM),indene-C60 bisadduct (ICBA), [6,6]-phenyl-C61-butyric acid methyl ester(PCBM), indene-C60 bisadduct (ICBA),poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), Tin Oxide(SnO₂), Zinc Oxide (ZnO), Titanium Oxide (TiO₂).

Utilizing a conductive tape 114 advantageously protects and increasesthe stability of a perovskite device 124 because the conductive tape 114can encapsulate the perovskite device 124. In a specific embodiment, theconductive tape 114 can include a copper conductive tape with nickelparticles disposed in the adhesive (commercially available as productnumber 16067-1, Ted Pella Inc.). In other embodiments, a conductive tape114 can also be implemented into a perovskite device 124 (e.g., a solarcell) with an inverted structure as an anode. For example, a perovskitedevice 124 structure may include a fluorine-doped tin oxide (FTO), anelectron transport layer, a perovskite film, a hole transport layer, anda conductive tape 114 that functions as an anode.

The stability of a perovskite device 124 including a laminatedconductive tape 114 may be increased compared to a device with atraditional metal electrode. A conductive tape 114 has an excellentlamination function that can effectively prevent a perovskite film 110from being exposed to ambient air, which air exposure can compromise theintegrity of the perokskite material leading to a decrease in theeffectiveness of the perovskite device 124. A conductive tape 114 canserve both as an electrode and a lamination or encapsulation layer.Further, the multifunction nature of a conductive tape 114 simplifiesdevice fabrication by omitting the metal electrode deposition processand the encapsulation process.

FIG. 6 illustrates a process 600 for fabricating a doctor-bladedperovskite device according to an embodiment. In one embodiment, aperovskite device structure formed according to process 600 includes anITO substrate (functioning as anode), a hole transport layer, aperovskite film 110 (e.g., MAPbI₃), an electron transport layer (e.g.,[6,6]-phenyl-C61-butyric acid methyl ester (PC₆₀BM), C₆₀, and/or2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)), and a cathode(e.g., Al, Ag, Cu or Au, etc.) layer. Process 600 may be performed in aN₂ atmosphere.

In step 602, an ITO substrate (e.g., an ITO coated glass substrate) isheated. Processing may begin by cleaning an ITO coated glass substrate,e.g., cleaning with deionized water, acetone, and UVO cleaner.Additionally, a hole transport layer may be deposited on, or otherwiseformed on, the ITO substrate. In one specific embodiment, a holetransport layer (e.g.,Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS),)can be applied to the ITO substrate and dried (e.g., in air at 135° C.for 20 min for PEDOT:PSS, or in N₂ at 100° C. for 10 min for PTAA). Inanother specific embodiment, a hole transport layer (e.g.,N,N′-Bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD) plus(z)-2-cyano-3-(4-(diphenylamino)phenyl) acrylic acid (TPACA)) can beapplied to the ITO substrate, e.g., by depositing a 15 nm thickTPD+TPACA layer with 0.25% by mass DCB solution onto the ITO substrateand cross-linking using a UV lamp and drying the TPD+TPACA (e.g., dryingin N₂ at 100° C. for 10 min). Heating the ITO substrate (e.g., ITO withhole transport layer) can include using at least one heating device 102.

In step 604, a perovskite precursor solution is dropped onto the ITOsubstrate. In certain embodiments, the perovskite precursor solutionincludes lead halide and methylammonium halide mixed indimethylformamide (DMF) or Methyl sulfoxide (DMSO). In one specificembodiment, a perovskite precursor solution is dropped onto an ITOsubstrate including hole transport materials. In a specific embodiment,10-20 μL of perovskite precursor solution can be dropped onto the ITOsubstrate for about every 2.25 mm² of ITO substrate. Other processes,such as spin coating, may use as much as 50-100 μL of the sameperovskite precursor solution over the same substrate area.

In embodiments, the perovskite precursor solution can include amethylammonium halide (MAH), such as methylammonium iodide (CH₃NH₃I,MAI), methylammonium bromide (CH₃NH₃Br, MABr), or methylammoniumchloride (CH₃NH₃Cl, MACl), or formamidinium halide (FAH), such asformamidinium iodide (CH(NH₃)₂I, FAI), formamidinium bromide(CH(NH₃)₂Br, FABr), or formamidinium chloride (CH(NH₃)₂Cl, FACl), andlead halide (PbI₂, PbBr₂, PbCl₂) dissolved in dimethylformamide (DMF) orMethyl sulfoxide (DMSO) or a mixture of the two in any ratio. In theseembodiments, a 1:1 molar ratio between lead halide and themethylammonium halide (or formamidinium halide) may be used, e.g., at amass ratio of 40% PbI₂ (e.g., 400 mg per 1 mL solvent) and 13.8%methylammonium halide.

In step 606, the perovskite precursor solution is doctor-bladed, e.g.,linearly swiped using a doctor blade, to form a perovskite film. In animplementation, the dropped perovskite precursor solution 118 (FIG. 2)can be swiped linearly by a doctor blade 116 (e.g., a glass blade) at aspeed of about 0.75 cm/s (27 m/hour) resulting in a smooth perovskitefilm 110. The doctor blade 116 functions to remove excess perovskiteprecursor solution and smooth the remaining perovskite precursorsolution. A high deposition (dropping and blading) speed is advantageouswhen fabricating large area perovskite devices with a high throughput.The thickness of the perovskite film 110 during doctor-blade coating maybe controlled by perovskite precursor solution concentration, bladingspeed, and the spacing of the doctor-blade relative to the ITOsubstrate. In certain embodiments, the ITO substrate should bemaintained at an elevated temperature during doctor-blade deposition forthe formation of a smooth, pin-hole free perovskite film 110.

As discussed above, during doctor-blade deposition, the substratetemperature may be an important parameter for creating uniform, smoothand pin-hole free perovskite films.

In step 608, the perovskite film 110 is thermoannealed and solventannealed. In one embodiment, the perovskite film 110 can besimultaneously thermoannealed and solvent annealed, which can facilitateinter-diffusion between layers. In a specific embodiment,thermoannealing and solvent annealing perovskite film 110 includesthermoannealing the perovskite film 110 at about 100° C. for about 10minutes to about 60 minutes and simultaneously solvent annealing theperovskite film 110 with about 10 μL of DMF. It is contemplated thatother heating temperatures and durations (e.g., several minutes toseveral hours) and other solvents and/or concentrations may be utilizedfor thermoannealing and/or solvent annealing of perovskite film 110.

In step 610, charge transport layer (e.g. PC₆₀BM) layer may be depositedonto the perovskite film. In one specific example, PC₆₀BM, dissolved in2% by weight 1,2-dichlorobenzene (DCB) solution, is applied to theperovskite film to form a PC₆₀BM layer. In some implementations,depositing the PC₆₀BM layer may include using a liquid solution droppingand/or a doctor-blading process. However, other deposition processes maybe utilized, such as spin coating. In step 612, the PC₆₀BM layer isthermoannealed. For example, the PC₆₀BM layer can be furtherthermoannealed at about 100° C. for about 10 minutes to 60 minuteswithout or with solvent (e.g. DCB) annealing. Thermoannealing can serveto further interdiffuse the layers and/or further stabilize the PC₆₀BMlayer.

In optional step 614, a fullerene layer is deposited on the PC₆₀BMlayer. In certain embodiments, a fullerene layer may be deposited on thePC₆₀BM layer using, for example, a thermal deposition process. In onespecific example, depositing a fullerene layer includes depositing a 20nm thick layer of C₆₀ and an 8 nm thick layer of BCP using thermalevaporation. It is contemplated that other fullerene materials and/orother layer thicknesses may be used.

In step 616, a conducting layer (e.g., including a conductive materialsuch as a metal layer) is then formed on the fullerene layer to functionas a cathode and/or an anode. In one embodiment, a metal layer can bedeposited, e.g., deposition of a metal layer (e.g., Ag, Al, Cu, Au, etc)on the fullerene layer using a sputtering process. In another specificembodiment, forming a conducting layer includes rolling and laminating aconductive tape 114 onto the fullerene layer and/or a perovskite film110.

In a specific embodiment, a perovskite device 124 may include a cathodelayer, an anode layer, and a halide perovskite layer (e.g., perovskitefilm 110) disposed between the cathode layer and the anode layer. Insome specific implementations, a semiconductor device and/or perovskitedevice 124 may include a first buffer layer, a second buffer layer, andone or more passivation layers (e.g., a single layer of fullerenes, amixture of fullerenes, a stacking layer of fullerenes, and/or othermaterial layers).

The cathode layer can include a cathode, which can include an electrodefrom which a conventional current leaves a polarized electrical device.The anode layer can include an anode, which can include an electrodethrough which positive electric charge flows into a polarized electricaldevice, such as the semiconductor device and/or perovskite device 124.One specific embodiment can include an anode layer (e.g., an ITO layer108) which itself may be disposed on a glass substrate and/or a siliconsubstrate and/or a flexible substrate, an active layer (e.g., perovskitelayer), and a cathode layer (e.g., an aluminum layer, a silver layer, agold layer, etc.) configured to be a top layer on the active layer(e.g., distal from the ITO substrate, glass substrate and/or siliconsubstrate). In another specific embodiment, an inverted deviceconfiguration can include a cathode layer (e.g., ITO layer) which may bedisposed on a glass substrate and/or silicon substrate and/or a flexiblesubstrate, an active layer, and an anode layer (e.g., a silver layer,gold layer, aluminum layer, etc) configured to be a top layer (e.g.,distal from the ITO layer, glass substrate and/or silicon substrate). Insome embodiments, the bottom layer (e.g., proximate to a glass substrateand/or a silicon substrate) can function as a transparent electrode(e.g., an ITO layer), and the top layer (e.g., distal from the glasssubstrate and/or silicon substrate) can function as an opaque electrode(e.g., an aluminum layer or a silver layer or a gold layer).

In some specific embodiments, the cathode layer can include an Al layerand/or a Ag layer that functions as a cathode, and the anode layer caninclude an indium-tin oxide (ITO) layer that functions as an anode. Inother specific embodiments, the cathode layer can include an indium-tinoxide (ITO) layer that functions as a cathode, and the anode layer caninclude an aluminum layer that functions as an anode. Other materialsmay also be used to form the cathode layer, such as calcium, magnesium,lithium, sodium, potassium, strontium, cesium, barium, iron, cobalt,nickel, copper, silver, zinc, tin, samarium, ytterbium, chromium, gold,graphene, an alkali metal fluoride, an alkaline-earth metal fluoride, analkali metal chloride, an alkaline-earth metal chloride, an alkali metaloxide, an alkaline-earth metal oxide, a metal carbonate, a metalacetate, and/or a combination of two or more of the above materials.Further, other materials may be used to form the anode layer (or atransparent electrode), such as fluorine-doped tin oxide (FTO),aluminum-doped zinc oxide (AZO), antimony-tin mixed oxide (ATO), aconductive polymer, a network of metal nanowire, a network of carbonnanowire, nanotube, nanosheet, nanorod, carbon nanotube, silvernanowire, or graphene. In some embodiments, the cathode layer can beformed first (e.g., disposed on a glass substrate and/or siliconsubstrate) while the anode layer is formed last (e.g., a cathode layeris formed on a glass substrate and the anode layer is formed last on abuffer layer). In another embodiment, the anode layer can be formedfirst while the cathode layer can be formed last (e.g., an anode layeris formed on a glass substrate and/or silicon substrate and the cathodelayer is formed last on a buffer layer).

The semiconductor device and/or perovskite device 124 can include anactive layer, which can include perovskite film 110. In implementations,the active layer serves to absorb light. In one specific example, anactive layer can be configured to absorb light having a wavelength in afirst predetermined range, and the anode layer may be transparent tolight having a wavelength in a second predetermined range, the secondpredetermined range overlapping the first predetermined range in a thirdpredetermined range. In this specific example, the semiconductor deviceand/or perovskite device 124 may have a high resistivity when notilluminated by any light and may have a low resistivity when illuminatedby light having a wavelength in the third predetermined range. In anembodiment, the active layer can include a perovskite film 110 (e.g., ahalide perovskite device), which can function as a photovoltaic materialand include a photovoltaic perovskite material (e.g., perovskite film110). The perovskite film 110 can be disposed between the cathode layerand the anode layer. In some specific embodiments, the perovskite film110 can include a continuous perovskite film that can be formed by theinterdiffusion of solution-deposited lead (II) iodide (PbI₂) andmethylammonium halide (CH₃NH₃X, where X can include Cl, Br, I) stackedpre-cursor layers. In these embodiments, the stacked pre-cursor layerscan subsequently be annealed to facilitate interdiffusion between thelayers. The resulting high quality perovskite film 110 allows thefabrication of leakage-free photovoltaic devices and a high PCE of15-17%.

In other embodiments, the active layer can include at least one ofpolyvinyl carbazole (PVK), poly(3-hexylthiophene) (P3HT),poly[4,8-bis-(2-ethyl-hexylthiophene-5-yl)-benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl]-alt-[2-(2′-ethyl-hexanoyl)-thieno[3,4-b]thiophen-4,6-diyl(PBDTTT-CT), phthalocyanine complex, a porphyrin complex, apolythiophene (PT), a derivative of polythiophene, a polycarbazole, aderivative of polycarbazole, a poly(p-phenylene vinylene) (PPV), aderivative of poly(p-phenylene vinylene), a polyfluorene (PF), aderivative of polyfluorene, a cyclopentadithiophene-based polymer, abenzodithiophene (BDT)-based polymer, poly(3-octylthiophene) (P30T),poly(3-hexyloxythiophene) (P3DOT), poly(3-methylthiophene) (PMeT),poly(3-dodecylthiophene) (P3DDT), poly(3-dodecylthienylenevinylene)(PDDTV), poly(3,3 dialkylquarterthiophene) (PQT),poly-dioctyl-fluorene-co-bithiophene (F8T2),poly-(2,5,-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene)(PBTTT-C12),poly[2,7-(9,9′-dihexylfluorene)-alt-2,3-dimethyl-5,7-dithien-2-yl-2,1,3-benzothiadiazole](PFDDTBT),poly{[2,7-(9,9-bis-(2-ethylhexyl)-fluorene)]alt-[5,5-(4,7-di-20-thienyl-2,1,3-benzothiadiazole)]}(BisEH-PFDTBT),poly{[2,7-(9,9-bis-(3,7-dimethyl-octyl)-fluorene)]-alt-[5,5-(4,7-di-20-thienyl-2,1,3-benzothiadiazole)]}(BisDMOPFDTBT),poly[N-9″-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′benzothiadiazole)](PCDTBT), and/or a combination of at least two of the above materials.

Additionally, a semiconductor device and/or the perovskite device 124may include a trapping layer, a first buffer layer, and/or a secondbuffer layer. The trapping layer, the first buffer layer, and/or thesecond buffer layer can be disposed between the active layer and thecathode layer and/or between the active layer and the anode layer. Inimplementations, the trapping layer can function as a carrier or chargetrapping layer (hole transporting/electron blocking layer) which caninclude at least one of zinc oxide (ZnOx), titanium oxide (TiOx), tinoxide (SnOx), zinc sulfide (ZnS), cadmium sulfide (CdS), lead sulfide(PbS), iron sulfide (FeS), iron pyrite (FeS2), cadmium selenide (CdSe),lead selenide (PbSe), cadmium telluride (CdTe), lead telluride (PbTe),Si, Ge, InAs, InSb, Pb_(1-x)Sn_(x)Te, Hg_(1-x)CdxTe, InAsSb, InNSb,InBiTe, InTlSb, InAs/GaInSb super lattice, HgTe/CdTe super lattice,graphene quantum dots, carbon nanotubes, and/or fullerene. Additionally,the trapping layer may include organic electron trapping particles,which can further include at least one of a fullerene, a derivative offullerene, a perylene derivative, a 2,7-dicyclohexyl benzo,phenanthroline derivative, a 1,4-diketo-3,6-dithienylpyrrolo[3,4-c]pyrrole (DPP) derivative, a tetracyanoquinodimethane (TCNQ)derivative, indene-C60 bisadduct ([60]ICBA), indene-C70 bisadduct([70]ICBA), a poly(p-pyridyl vinylene) (PPyV) derivative, a9,9′-bifluorenylidene (99BF) derivative, a benzothiadiazole (BT)derivative, [6,6]-phenyl C61-butyric acid methy ester (PC60BM),[6,6]-phenyl C71-butyric acid methyl ester (PC70BM),[6,6]-(4-fluoro-phenyl)C61-butyric acid methyl ester (FPCBM), carbon 60(C60), carbon 70 (C₇₀), fullerene self-assembly layer (C₆₀-SAM), carbonnanotubes (CNT), a carbon onion, and/or a combination of two or more ofthe above materials. In some embodiments, the trapping layer may beintegrated into a first buffer layer and/or a second buffer layer. In aspecific example, a second buffer layer can include a double fullerenelayer (e.g., [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) andindene-C₆₀ bisadduct (ICBA)) disposed between an active layer and ananode layer.

The first buffer layer and/or the second buffer layer can be formed onat least one side (e.g., anode side and/or the cathode side) of theperovskite film 110 and can function to passivate the perovskite surfaceand/or grain boundaries. In embodiments, the first buffer layer and/orthe second buffer layer may include at least one of an organic material,self-assembled monolayers (SAMs), poly(3,4-ethylenedioxithiophene)(PEDOT) doped with poly(styrene sulfonicacid) (PSS),Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA),4,4′bis[(ptrichlorosilylpropylphenyl)phenylamino]biphenyl (TPD-Si₂),poly(3-hexyl-2,5-thienylene vinylene) (P3HTV) and C60, copperphthalocyanine (CuPc), poly[3,4-(1hydroxymethyl)ethylenedioxythiophene](PHEDOT), n-dodecylbenzenesulfonic acid/hydrochloric acid-dopedpoly(aniline) nanotubes (a-PANIN)s, poly(styrenesulfonicacid)-graft-poly(aniline) (PSSA-g-PANI),poly[(9,9-dioctylfluorene)-co-N-(4-(l-methylpropyl)phenyl)diphenylamine](PFT), 4,4′bis[(p-trichlorosilylpropylphenyl)phenylamino]biphenyl(TSPP), 5,5′-bis[(ptrichlorosilylpropylphenyl)phenylamino]-2,20-bithiophene (TSPT), N-propyltriethoxysilane,3,3,3-trifluoropropyltrichlorosilane or 3-aminopropyltriethoxysilane,V₂O₅, VOx, MoO₃, WO₃, ReO₃, NiOx, AgOx/PEDOT:PSS, Cu₂O, CuSCN/P3HT,and/or Au nanoparticles.

In some embodiments, a second buffer layer may include at least one ofan alkali metal compound, a metal oxide, an organic material,self-assembled mono layers (SAMs), LiF, CsF, LiCoO₂, Cs₂CO₃, TiOx, TiO₂nanorods (NRs), ZnO, ZnO nanorods (NRs), ZnO nanoparticles (NPs), ZnO,Al₂O₃, CaO, bathocuproine (BCP), copper phthalocyanine (CuPc),pentacene, pyronin B, [6,6]-phenyl C61-butyric acid methyl ester (PCBM),[6,6]-phenyl C61-butyric acid methyl ester (PC70BM),pentadecafluorooctyl phenyl-C₆₀-butyrate (F-PCBM), C₆₀, C₆₀/LiF, ZnONRs/PCBM, ZnO/cross-linked fullerene derivative (C-PCBSD), single walledcarbon nanotubes (SWCNT), poly(ethylene glycol) (PEG),poly(dimethylsiloxaneblock-methyl methacrylate) (PDMS-b-PMMA), polarpolyfluorene (PF-EP), polyfluorene bearing lateral amino groups (PFN),polyfluorene bearing quaternary ammonium groups in the side chains(WPF-oxy-F), polyfluorene bearing quaternary ammonium groups in the sidechains (WPF-6-oxy-F), fluorene alternating and random copolymer bearingcationic groups in the alkyl side chains (PFNBr-DBTI5), fluorenealternating and random copolymer bearing cationic groups in the alkylside chains (PFPNBr), or poly(ethylene oxide) (PEO). In one specificembodiment, the second buffer layer includes at least one layer of C₆₀,PCBM, and/or ICBA.

In one specific embodiment, a semiconductor device and/or the perovskitedevice 124 includes a structure including a cathode layer includingIndium-Tin oxide formed on a glass substrate, a first buffer layerincluding poly(3,4-ethylenedioxythiophene) poly(styrenesulphonate)(PEDOT:PSS) disposed on the cathode layer, an active layer and aperovskite film 110 including MAPbI₃ (e.g., iodine perovskite) formed onthe first buffer layer, a trapping layer and second buffer layerincluding [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM with about a20 nm thickness) or indene-C_(x) bisadduct (ICBA), C₆₀ (e.g., about a 20nm thickness), and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP,with about a 7 nm thickness) formed on the active layer, and an anodelayer including aluminum (with a thickness of about 100 nm) formed onthe trapping layer and second buffer layer. In this specific embodiment,a perovskite precursor solution may be formed on the semiconductordevice and/or the perovskite device 124 separately or as a pre-mixedprecursor. This configuration can result in a continuous, pin-hole freeperovskite film 110 with a film thickness variation often less than 20nm. After an annealing process, the semiconductor device and/or theperovskite device 124 results in a layered structure with penetration ofPb and I across the whole perovskite layer. In one instance, the depthprofile of Pb and I may include a graded composition with increased Pband I toward the PEDOT:PSS side. The perovskite-based semiconductordevice and/or the perovskite device 124 can function as a highlysensitive UV and visible light photo detector. In another specificembodiment, the semiconductor device and/or the perovskite device 124can include an anode layer (e.g., Al) and a first buffer layer includinga layer of ITO, a perovskite film 110 on the anode layer and the firstbuffer layer, a trapping layer including TPD-Si₂ disposed on theperovskite film 110, a second buffer layer including MoO₃ disposed onthe trapping layer, and a cathode layer (e.g., ITO) disposed on thetrapping layer.

Some halide perovskite materials can only absorb light up to about 800nm, and thus may not have light detection ability in the near-IR range.In one implementation, a quantum dots (QDs) halide perovskite hybridsemiconductor device can extend light detection to near-IR range. Inthis implementation, the semiconductor device can include an activelayer including quantum dots, which can be operated as sensitizers whilethe halide perovskite layer can serve as a functional interface fromwhich to extract carriers and also as bridges to transfer carriersbetween quantum dots. In these implementations, PbS quantum dots can beintegrated into a first buffer layer and/or a second buffer layerincluding a PCBM to form a PCBM matrix. This specific semiconductordevice can function as a highly sensitive board wavelength photodetector.

Some fabrication processes include methods for forming continuous and/orcompact lead iodine perovskite (MAPbI₃) films by the interdiffusion offormed and/or spin-coated layers of stacked PbI₂ and MAI. The resultinghigh quality perovskite film can allow for the fabrication ofleakage-free photovoltaic devices and a high PCE of 15-17%. In thesefabrication processes, a lead iodine (PbI₂) layer can be formed on acathode layer, and a methylammonium halide (MAI) layer can be formed onthe lead iodine layer. In other embodiments, the precursors (e.g., MAIand PbI₂) can be pre-mixed prior to applying and/or spin-coating theperovskite film on a first buffer layer, a cathode layer, and/or ananode layer. It is contemplated that other lead-based layers can beformed (e.g., PbX₂, where X can be Br, Cl, etc.). In a specificimplementation, PbI₂ and MAI can be dissolved in dimethylformamide (DMF)and 2-propanol, respectively, as precursor solutions at variedconcentrations. The respective precursor solutions can then be formed,dropped, and/or spun onto a substrate, such as a glass substrate and/ora first buffer layer. In some implementations, the glass substrate 106can include a first buffer layer, such aspoly(3,4-ethylenedioxythiophene) poly(styrenesulphonate) (PEDOT:PSS).Additionally, the glass substrate may be covered with a cathode layer,such as indium tin oxide (ITO). In other implementations, the glasssubstrate may include an anode layer instead of a cathode layer, such asan aluminum layer. In some implementations, the PbI₂ layer may be formedfirst and disposed under the MAI layer. In other implementations the MAIlayer may be formed first and disposed under the PbI₂ layer. In someembodiments, a supersaturated hot solution of PbI₂ may be used for quickdrying to obtain a pin-hole free and conformal PbI₂ layer on a PEDOT:PSSlayer and/or a glass substrate. Since PbI₂ has relatively low solubilityin 2-propanol, the spin-coating of MAI will not wash off PbI₂.

In one implementation for forming a lead iodide (PbI₂) layer and amethylammonium halide (MAI) layer, a CH₃NH₃I precursor is synthesized.In a specific example, a concentrated aqueous solution of hydroiodicacid (HI) (e.g., 15.0 mL, 57 wt % in water) can be reacted withmethylamine (CH₃NH₂) (e.g., 13.5 mL, 40 wt % in aqueous solution) at 0°C. for 2 hours with constant stirring under a nitrogen atmosphere.Methylammonium can then be crystalized by removing the solvent using arotary evaporator. In this specific example, the resulting white powdercan be washed with diethyl ether (e.g., three times) and dried in avacuum.

In a specific implementation (e.g., for fabricating a solar cell), PbI₂and/or MAI can be dissolved in DMF and 2-propanol with varyingconcentrations from about 130 mg/ml to about 450 mg/ml for PbI₂, andfrom about 17.5 mg/ml to about 50 mg/ml for MAI, respectively. Inanother specific implementation (e.g., for fabricating a photodetector),concentrations can include about 400-800 mg/ml for PbI₂ and about 15-60mg/ml for MAI. In some implementations, the CH₃NH₃X and PbX₂ precursormixture solutions dissolved in dimethylformamide (DMF) can includevaried PbI₂/CH₃NH₃I precursor molar ratios (defined as a precursorratio) from about 0.35 to about 1.5. The thickness of the CH₃NH₃PbI₃films (e.g., from about 80 nm to about 5,000 nm) may be determined byvarying the concentration of the precursor solutions. In one specificexample, the precursor solutions can have a precursor ratio betweenabout 0.5 to about 0.9, which may result in an iodine perovskitethickness of between about 200-500 nm. In some embodiments, a thickerperovskite film of about 1,000-8,000 nm may be used for mixed halideperovskites. In some implementations, the temperature of the precursorsolution(s) can be generally above room temperature. A highconcentration precursor solution may be used to form a relativelythicker perovskite film. In this specific embodiment, both solutions maybe heated at about 100° C. for approximately 10 min before use to ensurethat both the MAI and PbI₂ are fully dissolved. The PbI₂ solution can besubsequently formed and/or spun on a PEDOT:PSS layer or other substrateat about 70° C. at 6,000 round per second (rpm) for 35 seconds. Then,the PbI₂ film can be quickly transferred onto a hot plate and dried atabout 70° C. The MAI solution can be spun on top of the dried PbI₂ filmat 6,000 rpm for 35 seconds at room temperature in order to form a filmwith thickness ranging from about 70-320 nm. The MAI layer thickness maydepend the precursor solution concentration as well as the thickness ofthe underlying PbI₂ layer. The spin coated PbI₂ and MAI stacking filmsmay then be dried at about 100° C. from one to three hours. In thisspecific implementation, a PCBM layer (e.g., dissolved inDichlorobenzene (DCB), (e.g., 2 wt. %) may be spun on the formedperovskite layers after cooling to room temperature.

The lead iodine layer and the methylammonium halide layer may then beannealed to form an interdiffused perovskite film 110. Inimplementations, the PbI₂ and MAI layers can be solvent annealed and/orthermally annealed for varied durations. In one example of thermalannealing, the PbI₂ and MAI layers can be annealed at a temperature ofabout 80-120° C. for about 30-180 mins. In a specific example of solventannealing, about 10 μL of DMF solvent can be added proximate to the PbI₂and MAI layers during the thermal annealing process such that the DMFvapor can contact the perovskite layer. The DMF vapor may penetrate intothe perovskite film and facilitate the growth of crystalline domains.The resulting annealed perovskite film 110 may be generally continuousand pinhole-free across the whole surface. In contrast, bilayer MAPbI₃films formed and spun from premixed PbI₂ and MAI blend solutionsgenerally may be non-uniform with many microstructures on the surface.In one specific embodiment, a PbI₂, MAI, and PCBM layer can be annealedat 100° C. for one hour to let the PCBM crystalize and/or diffuse into aresulting perovskite layer. In another specific embodiment, a mixedhalide perovskite layer may be annealed for about 2 hours. In someinstances, the perovskite film 110 may be finished by forming additionallayers (e.g, a second buffer layer, a trapping layer, etc.). In aspecific example, a fullerene layer can be formed using thermalevaporating (e.g., C₆₀ (20 nm), BCP (8 nm)).

An anode layer can then be formed on the perovskite film 110. Inimplementations, the anode layer can be formed on the perovskite film110, second buffer layer, and/or trapping layer using processes such asphysical vapor deposition. In a specific embodiment, an aluminum anodecan be formed to a thickness of about 100 nm. In another specificembodiment, the semiconductor device and/or perovskite device 124 areacan be defined to be the overlap of the cathode layer (e.g., ITO) andanode layer (e.g., an aluminum electrode) to be about 6 mm².

U.S. application Ser. No. 14/576,878, filed Dec. 19, 2014, entitled“Photovoltaic Perovskite Material and Method of Fabrication,” providesadditional detail regarding device materials and processes and is herebyincorporated by reference herein for all purposes.

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference to the sameextent as if each reference were individually and specifically indicatedto be incorporated by reference and were set forth in its entiretyherein.

The use of the terms “a” and “an” and “the” and “at least one” andsimilar referents in the context of describing the disclosed subjectmatter (especially in the context of the following claims) are to beconstrued to cover both the singular and the plural, unless otherwiseindicated herein or clearly contradicted by context. The use of the term“at least one” followed by a list of one or more items (for example, “atleast one of A and B”) is to be construed to mean one item selected fromthe listed items (A or B) or any combination of two or more of thelisted items (A and B), unless otherwise indicated herein or clearlycontradicted by context. The terms “comprising,” “having,” “including,”and “containing” are to be construed as open-ended terms (i.e., meaning“including, but not limited to,”) unless otherwise noted. Recitation ofranges of values herein are merely intended to serve as a shorthandmethod of referring individually to each separate value falling withinthe range, unless otherwise indicated herein, and each separate value isincorporated into the specification as if it were individually recitedherein. All methods described herein can be performed in any suitableorder unless otherwise indicated herein or otherwise clearlycontradicted by context. The use of any and all examples, or examplelanguage (e.g., “such as”) provided herein, is intended merely to betterilluminate the disclosed subject matter and does not pose a limitationon the scope of the invention unless otherwise claimed. No language inthe specification should be construed as indicating any non-claimedelement as essential to the practice of the invention.

Certain embodiments are described herein. Variations of thoseembodiments may become apparent to those of ordinary skill in the artupon reading the foregoing description. The inventors expect skilledartisans to employ such variations as appropriate, and the inventorsintend for the embodiments to be practiced otherwise than asspecifically described herein. Accordingly, this disclosure includes allmodifications and equivalents of the subject matter recited in theclaims appended hereto as permitted by applicable law. Moreover, anycombination of the above-described elements in all possible variationsthereof is encompassed by the disclosure unless otherwise indicatedherein or otherwise clearly contradicted by context.

What is claimed:
 1. A process for fabricating a perovskite device,comprising: receiving a substrate; applying a perovskite precursorsolution onto the substrate; linearly swiping the perovskite precursorsolution using a doctor blade to form a perovskite device including aperovskite film on the substrate; heating the perovskite device; androlling a conductive tape onto the perovskite device, wherein theconductive tape includes an adhesive material and a conductive material.2. The process of claim 1, further comprising: simultaneously heatingthe substrate while applying and linearly swiping the perovskiteprecursor solution.
 3. The process of claim 1, wherein the substrate ismoving and the doctor blade is stationary.
 4. The process of claim 1,wherein the substrate is moving at a rate of about 0.75 to about 75cm/sec relative to the doctor blade.
 5. The process of claim 1, whereinthe substrate is stationary and wherein the doctor blade moves relativeto the substrate.
 6. The process of claim 1, wherein applying theperovskite precursor solution onto the substrate includes dispensingbetween about 10 μL and about 20 μL of perovskite precursor solution forevery 2.25 mm² of substrate.
 7. The process of claim 1, wherein theprecursor solution includes a lead halide and at least one of amethylammonium halide or a formamidinium halide dissolved indimethylformamide (DMF) or Methyl sulfoxide (DMSO).
 8. The process ofclaim 1, wherein the substrate comprises indium tin oxide (ITO) or othertransparent conductive electrode material.
 9. The process of claim 1,wherein heating the perovskite device includes heating the perovskitedevice to a temperature between about 50° C. and about 175° C.
 10. Theprocess of claim 1, wherein the substrate comprises indium tin oxide(ITO) or other transparent conductive electrode material.
 11. Theprocess of claim 2, wherein heating the substrate includes heating thesubstrate to a temperature in a range of between about 50° C. and about180° C.
 12. The process of claim 11, wherein heating the substrateincludes heating the substrate to about 125° C.
 13. A process forcontinuously laminating a perovskite device, comprising: forming aperovskite device by doctor blade coating a perovskite precursorsolution onto a substrate; heating the perovskite device; and rolling aconductive tape onto the perovskite device, wherein the conductive tapeincludes an adhesive material and a conductive material.
 14. The processof claim 13, wherein heating the perovskite device includes heating theperovskite device to a temperature between about 50° C. and about 175°C.
 15. The process of claim 13, wherein the conductive material includesat least one of aluminum, copper, nickel, gold, or silver.
 16. A processfor fabricating perovskite device, comprising: heating an indium tinoxide (ITO) substrate; applying a perovskite precursor solution onto theITO substrate; linearly swiping the perovskite precursor solution usinga doctor blade to form a perovskite film; simultaneously thermoannealingand solvent annealing the perovskite film; depositing a charge transportlayer on the perovskite film; thermoannealing the charge transportlayer; depositing a fullerene layer on the charge transport layer; andapplying a conductive layer to the fullerene layer.
 17. The process ofclaim 16, wherein the ITO substrate includes an ITO layer and a holetransport layer.
 18. The process of claim 16, wherein the precursorsolution includes a lead halide (PbI₂, PbBr₂ or PbCl₂) and at least oneof methylammonium halide (CH₃NH₃I, CH₃NH₃Br, CH₃NH₃Cl) or formamidiniumhalide (CH(NH₂)₂I, CH(NH₂)₂Br, CH(NH₂)₂Cl) dissolved indimethylformamide (DMF) or Methyl sulfoxide (DMSO) or a mixture thereofin any ratio.
 19. The process of claim 17, wherein the hole transportlayer includes at least one of PEDOT:PSS, TPD plus TPACA or PTAA, orother hole transport material or materials.